JPH05124817A - Formation of thin barium titanate film - Google Patents
Formation of thin barium titanate filmInfo
- Publication number
- JPH05124817A JPH05124817A JP31549791A JP31549791A JPH05124817A JP H05124817 A JPH05124817 A JP H05124817A JP 31549791 A JP31549791 A JP 31549791A JP 31549791 A JP31549791 A JP 31549791A JP H05124817 A JPH05124817 A JP H05124817A
- Authority
- JP
- Japan
- Prior art keywords
- barium titanate
- thin film
- aqueous solution
- titanium
- substrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910002113 barium titanate Inorganic materials 0.000 title claims abstract description 37
- 230000015572 biosynthetic process Effects 0.000 title abstract description 3
- 239000010936 titanium Substances 0.000 claims abstract description 26
- 239000000758 substrate Substances 0.000 claims abstract description 19
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 17
- 239000010409 thin film Substances 0.000 claims description 40
- 239000007864 aqueous solution Substances 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 18
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- 150000004703 alkoxides Chemical class 0.000 claims description 8
- 229910052788 barium Inorganic materials 0.000 claims description 6
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- 239000000463 material Substances 0.000 abstract description 28
- -1 titanium alkoxide Chemical class 0.000 abstract description 8
- 229910001422 barium ion Inorganic materials 0.000 abstract description 2
- 239000007769 metal material Substances 0.000 abstract description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical class [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000007654 immersion Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N monoethanolamine hydrochloride Natural products NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 3
- 230000006911 nucleation Effects 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000015654 memory Effects 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 239000013212 metal-organic material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02172—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
- H01L21/02197—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides the material having a perovskite structure, e.g. BaTiO3
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
- H01L21/02282—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process liquid deposition, e.g. spin-coating, sol-gel techniques, spray coating
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/314—Inorganic layers
- H01L21/316—Inorganic layers composed of oxides or glassy oxides or oxide based glass
- H01L21/31691—Inorganic layers composed of oxides or glassy oxides or oxide based glass with perovskite structure
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/01—Manufacture or treatment
- H10N30/07—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base
- H10N30/074—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base by depositing piezoelectric or electrostrictive layers, e.g. aerosol or screen printing
- H10N30/077—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base by depositing piezoelectric or electrostrictive layers, e.g. aerosol or screen printing by liquid phase deposition
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/80—Constructional details
- H10N30/85—Piezoelectric or electrostrictive active materials
- H10N30/853—Ceramic compositions
- H10N30/8536—Alkaline earth metal based oxides, e.g. barium titanates
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Ceramic Engineering (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Inorganic Insulating Materials (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】この発明は、強誘電体薄膜の形成
方法、詳しくは、種々の基材上に強誘電体であるチタン
酸バリウムの薄膜を、複雑な工程によることなく、簡便
に形成する方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a ferroelectric thin film, and more specifically, to easily form a thin film of barium titanate, which is a ferroelectric, on various substrates without complicated steps. On how to do.
【0002】[0002]
【従来の技術】チタン酸バリウム(BaTiO3)は、
強誘電体材料、圧電体材料、焦電体材料として優れた性
質を有し、超音波センサ、コンデンサ、アクチュエー
タ、焦電型赤外線センサ、不揮発性メモリーなどの種々
のデバイスに幅広く利用されており、さらに多くの分野
への応用が試みられている。そして、チタン酸バリウム
をこれらのデバイスに応用する場合、その特性を有効に
利用するために、チタン酸バリウムを薄膜として用いる
ことが一般的である。2. Description of the Related Art Barium titanate (BaTiO 3 ) is
It has excellent properties as a ferroelectric material, piezoelectric material, and pyroelectric material, and is widely used in various devices such as ultrasonic sensors, capacitors, actuators, pyroelectric infrared sensors, and non-volatile memories. Application to more fields is being tried. When barium titanate is applied to these devices, it is common to use barium titanate as a thin film in order to effectively utilize its characteristics.
【0003】そして、基材上にチタン酸バリウム(Ba
TiO3)薄膜を形成する方法としては、従来より、 基材でもあるチタン金属表面を化成処理する方法(例
えば、特開昭61−30678号)、 スパッタ蒸発したターゲット物質を基板(基材)上に
沈着させて薄膜を形成するスパッタリング法(例えば、
特開平2−94209号)によるもの、 プラズマを利用して薄膜を形成するプラズマ蒸着法に
よるもの(例えば、特開平2−258700号)、 湿式の薄膜形成方法である水熱電気化学法によるもの
(例えば、JJAPVol.28 No.11(198
9))、 など種々の形成方法が知られている。Then, barium titanate (Ba
As a method for forming a TiO 3 ) thin film, conventionally, a method of subjecting a titanium metal surface, which is also a base material, to chemical conversion treatment (for example, Japanese Patent Laid-Open No. 61-30678), a sputter-evaporated target material on a substrate (base material) is used. Sputtering method to deposit a thin film to form a thin film (for example,
JP-A-2-94209), a plasma deposition method for forming a thin film using plasma (for example, JP-A-2-258700), a hydrothermal electrochemical method that is a wet thin film forming method ( For example, JJAP Vol. 28 No. 11 (198
9)), etc. are known.
【0004】[0004]
【発明が解決しようとする課題】しかし、上記従来のB
aTiO3薄膜の形成方法には、それぞれ次のような問
題点がある。すなわち、 のチタン金属表面を化成処理する方法は、基材がチタ
ン金属に限定され、チタン以外の材料を基材として用い
る場合には適用することができない、 のスパッタリング法は、複雑で高価な装置を必要と
し、設備費用が大きくなる、 のプラズマ蒸着法は、複雑で大掛かりな装置を必要と
し、さらに、高温に耐える基材にしか適用できない、 の水熱電気化学法は、基材自体を電極として用いるた
め、良導性の金属基材にしか適用することができず、ま
た、オートクレーブを用いて高温高圧下で成膜するた
め、耐熱性の小さい有機基材には適用できない、 など種々の問題点を包含している。However, the above-mentioned conventional B
Each of the methods of forming an aTiO 3 thin film has the following problems. That is, the method for chemical conversion treatment of titanium metal surface is limited to titanium metal as a base material and cannot be applied when a material other than titanium is used as the base material. The sputtering method is a complicated and expensive apparatus. The plasma deposition method requires a complicated and large-scale device, and can be applied only to a base material that can withstand high temperatures. The hydrothermal electrochemical method uses the base material itself as an electrode. Therefore, it can be applied only to a metal substrate having good conductivity, and it is not applicable to an organic substrate having low heat resistance because the film is formed under high temperature and high pressure using an autoclave. It contains problems.
【0005】この発明は上記問題点を解決するものであ
り、複雑で大掛かりな設備や、厳しい成膜条件を必要と
することなく、無機材料、金属材料、有機材料及びこれ
らの複合材料などの種々の材料からなる基材の表面にチ
タン酸バリウム薄膜を簡便に形成することが可能なチタ
ン酸バリウム薄膜の形成方法を提供することを目的とす
る。The present invention solves the above-mentioned problems, and various inorganic materials, metal materials, organic materials, and composite materials of these materials can be used without requiring complicated and large-scale equipment and severe film forming conditions. An object of the present invention is to provide a method for forming a barium titanate thin film, which enables a barium titanate thin film to be easily formed on the surface of a base material made of the above material.
【0006】[0006]
【課題を解決するための手段】チタン酸バリウムの湿式
製造方法としては、チタンのアルコキシドを加水分解さ
せてバリウムと低温で反応させることにより、チタン酸
バリウムの粉体を得る方法が知られている。発明者等
は、この方法を様々な角度から検討するとともに、鋭意
実験研究を行い、チタンのアルコキシドの加水分解速度
を抑制することにより、生成するチタン酸バリウムが粉
体とならずに、薄膜となることを知り、この発明を完成
した。As a wet method for producing barium titanate, a method is known in which a barium titanate powder is obtained by hydrolyzing a titanium alkoxide and reacting it with barium at a low temperature. .. The present inventors have studied this method from various angles and conducted extensive experimental research to suppress the hydrolysis rate of titanium alkoxides, so that the produced barium titanate does not become a powder but forms a thin film. I found out that I completed this invention.
【0007】すなわち、この発明のチタン酸バリウム薄
膜の形成方法は、バリウム(Ba)イオン及びチタン
(Ti)のアルコキシドを含有する水溶液に基材を浸漬
することにより、該基材の表面にチタン酸バリウム薄膜
を形成することを特徴としている。That is, in the method for forming a barium titanate thin film of the present invention, the base material is immersed in an aqueous solution containing barium (Ba) ions and titanium (Ti) alkoxide, so that the surface of the base material is titanic acid. The feature is that a barium thin film is formed.
【0008】上記水溶液としては、バリウム(Ba)及
びチタン(Ti)のアルコキシドをそれぞれ、Ba2+,
Ti(IV)に換算して、 Ba2+ :0.01〜150mM/l Ti(IV):0.01〜500mM/l の範囲で含有させることが好ましい。As the above aqueous solution, barium (Ba) and titanium (Ti) alkoxides are added to Ba 2+ and Ba 2+ , respectively.
In terms of Ti (IV), it is preferable to contain Ba 2+ in the range of 0.01 to 150 mM / l Ti (IV): 0.01 to 500 mM / l.
【0009】また、上記水溶液の温度は、50〜110
℃の範囲にあることが好ましい。The temperature of the aqueous solution is 50 to 110.
It is preferably in the range of ° C.
【0010】また、上記水溶液のpHは、13以上であ
ることが好ましい。The pH of the aqueous solution is preferably 13 or more.
【0011】さらに、上記チタン(Ti)のアルコキシ
ドとしては、アルカノールアミン変性したアルコキシド
を用いることが好ましい。Further, it is preferable to use an alkanolamine-modified alkoxide as the titanium (Ti) alkoxide.
【0012】この発明のチタン酸バリウム薄膜の形成方
法における薄膜形成のメカニズムは、概略以下のように
説明される。すなわち、チタンのアルコキシドの加水分
解速度、水溶液のイオン濃度、水溶液の温度、pHなど
の諸条件が適当な領域にあるとき、チタン酸バリウム
は、水溶液中で沈殿(すなわち粉体)を生じるような均
一核形成を行わず、水溶液中に浸漬した基材の表面及び
容器の壁面などの固体表面で不均一核形成を行い、その
核が成長することによって、チタン酸バリウムの薄膜を
形成する。The mechanism of thin film formation in the method for forming a barium titanate thin film of the present invention will be described as follows. That is, when various conditions such as the hydrolysis rate of titanium alkoxide, the ion concentration of the aqueous solution, the temperature of the aqueous solution, and the pH are in appropriate ranges, barium titanate is likely to cause precipitation (that is, powder) in the aqueous solution. Without uniform nucleation, heterogeneous nucleation is performed on the surface of the substrate immersed in the aqueous solution and on the solid surface such as the wall surface of the container, and the nuclei grow to form a thin film of barium titanate.
【0013】したがって、この発明のチタン酸バリウム
薄膜の形成方法によれば、組成を調整した水溶液に基材
を浸漬するだけで、複雑な工程を必要とすることなく、
基材の表面に均一なチタン酸バリウム薄膜を形成するこ
とができる。Therefore, according to the method for forming a barium titanate thin film of the present invention, the base material is simply immersed in an aqueous solution having a adjusted composition, without requiring complicated steps.
A uniform barium titanate thin film can be formed on the surface of a base material.
【0014】[0014]
【実施例】以下に、この発明の実施例を比較例とともに
示して、発明の特徴をさらに詳しく説明する。EXAMPLES The features of the present invention will be described in more detail below by showing examples of the present invention together with comparative examples.
【0015】表1は、この発明の実施例及び比較例にお
ける水溶液(浸漬液)の組成や水溶液の温度(液温)な
どの薄膜形成条件を示す表である。なお、表1において
*印を付した試験番号1,2は、この発明の範囲外の比
較例の薄膜形成条件を示すものである。Table 1 is a table showing thin film forming conditions such as the composition of the aqueous solution (immersion liquid) and the temperature of the aqueous solution (liquid temperature) in Examples and Comparative Examples of the present invention. In Table 1, the test numbers 1 and 2 marked with * indicate the thin film forming conditions of the comparative examples outside the scope of the present invention.
【0016】[0016]
【表1】 [Table 1]
【0017】この実施例及び比較例では、各成分が表1
に示す濃度になるように、試薬特級の硝酸バリウム、エ
タノ−ルアミン変性チタンブトキシド(TBEA)及び
水酸化カリウムを、イオン交換水に溶解して浸漬液を調
製する。なお、エタノ−ルアミン変性チタンブトキシド
は、チタンブトキシドの4つのブトキシ基の一部または
全部をエタノ−ルアミンで置換したものを用いている。In the examples and comparative examples, each component is shown in Table 1.
A special grade barium nitrate, ethanolamine modified titanium butoxide (TBEA) and potassium hydroxide are dissolved in ion-exchanged water to prepare a dipping solution so that the concentration becomes as shown in FIG. As the ethanolamine-modified titanium butoxide, titanium butoxide in which some or all of the four butoxy groups are substituted with ethanolamine is used.
【0018】なお、チタンのアルコキシドとしては、チ
タンブトキシドに限られるものではなく、チタンエトキ
シドやチタンプロポキシドなど他のチタンアルコキシド
を用いることが可能である。The titanium alkoxide is not limited to titanium butoxide, and other titanium alkoxides such as titanium ethoxide and titanium propoxide can be used.
【0019】また、アルカノールアミン変性したチタン
ブトキシドとしては、エタノ−ルアミン変性したものに
限らず、例えば、プロパノールアミンなどの他のアルカ
ノールアミンで変性したチタンブトキシドを用いること
も可能である。The alkanolamine-modified titanium butoxide is not limited to ethanolamine-modified titanium butoxide, and, for example, titanium butoxide modified with other alkanolamines such as propanolamine can be used.
【0020】上記水溶液のpHは、水酸化カリウムの添
加量を増減することによって調整する。また、加水分解
速度を一定に保つために、上記水溶液にトリエタノ−ル
アミンを5vol%添加する。The pH of the aqueous solution is adjusted by increasing or decreasing the amount of potassium hydroxide added. Further, in order to keep the hydrolysis rate constant, 5 vol% of triethanolamine is added to the above aqueous solution.
【0021】このようにして調製された水溶液(浸漬
液)100mlをフッ素樹脂(テフロン)容器に入れ、こ
れに10×15×2mmの大きさのアルミナ焼結体、スラ
イドガラス及び白金からなる各基板を浸漬し、表1に示
す液温で20時間保持して反応を行わせた。100 ml of the thus-prepared aqueous solution (immersion liquid) was placed in a fluororesin (Teflon) container, and each substrate made of an alumina sintered body having a size of 10 × 15 × 2 mm, a slide glass and platinum. Was immersed in the solution and held at the liquid temperature shown in Table 1 for 20 hours to cause the reaction.
【0022】その結果、試験番号1,2(浸漬液の組成
がこの発明の範囲外である比較例)以外の試料について
は、基板表面に均一なチタン酸バリウム薄膜が形成され
ていることが認められた。As a result, it was confirmed that a uniform barium titanate thin film was formed on the surface of the substrate in samples other than Test Nos. 1 and 2 (comparative examples in which the composition of the immersion liquid was outside the scope of the present invention). Was given.
【0023】一方、Ba2+イオンまたは、エタノ−ルア
ミン変性チタンブトキシドの濃度が0.01mM/l未満
(試験番号1(Ba2+=0.005mM/l)及び試験番号
2(TBEA=0.005mM/l))になると均一な薄膜
が形成されなかった。また、表1には示していないが、
Ba2+イオンの濃度が150mM/lを越えた場合(例え
ば、Ba2+=300mM/l))及びエタノ−ルアミン変性
チタンブトキシドの濃度が500mM/lを越えた場合(例
えば、TBEA=700mM/l))には、水溶液中で均一
核形成が行われて直接沈殿が生成してしまい、チタン酸
バリウムの薄膜は形成されなかった。On the other hand, the concentration of Ba 2+ ion or ethanolamine-modified titanium butoxide was less than 0.01 mM / l (test number 1 (Ba 2+ = 0.005 mM / l) and test number 2 (TBEA = 0. 005 mM / l)), a uniform thin film was not formed. Also, although not shown in Table 1,
When the concentration of Ba 2+ ions exceeds 150 mM / l (for example, Ba 2+ = 300 mM / l) and when the concentration of ethanolamine-modified titanium butoxide exceeds 500 mM / l (for example, TBEA = 700 mM / l) In l)), uniform nucleation was carried out in the aqueous solution and direct precipitation was generated, and a thin film of barium titanate was not formed.
【0024】したがって、水溶液(浸漬液)の成分濃度
としては、Ba2+イオンが0.01〜150mM/l 、エ
タノ−ルアミン変性チタンブトキシドが0.01〜50
0mM/lの範囲にあることが好ましい。Therefore, the concentration of the components in the aqueous solution (immersion solution) is 0.01 to 150 mM / l for Ba 2+ ions and 0.01 to 50 for ethanolamine-modified titanium butoxide.
It is preferably in the range of 0 mM / l.
【0025】また、水溶液の温度が50℃未満になると
結晶質のチタン酸バリウム薄膜が得られず、また、水溶
液の温度が110℃を越えると気泡が基板表面に付着
し、薄膜の連続性、均一性が急激に悪化する。したがっ
て、水溶液の温度は、50〜110℃の範囲に調整する
ことが好ましい。Further, when the temperature of the aqueous solution is less than 50 ° C., a crystalline barium titanate thin film cannot be obtained, and when the temperature of the aqueous solution exceeds 110 ° C., bubbles adhere to the surface of the substrate, and the continuity of the thin film, Uniformity deteriorates sharply. Therefore, the temperature of the aqueous solution is preferably adjusted within the range of 50 to 110 ° C.
【0026】さらに、水溶液のpHが13未満になると
チタン酸バリウム以外の相が析出するため、水溶液のp
Hは13以上であることが好ましい。Further, when the pH of the aqueous solution becomes less than 13, a phase other than barium titanate precipitates.
H is preferably 13 or more.
【0027】なお、上記実施例においては、チタン酸バ
リウム薄膜を形成する基材として、アルミナ焼結体、ス
ライドガラス及び白金からなる各基板を用いた場合につ
いて説明したが、この発明は、これら以外の材料からな
る基板や、さらには、基板以外のフォイルなどを基材と
して、これにチタン酸バリウム薄膜を形成する場合に広
く適用することができる。In the above embodiment, the case where each substrate made of the alumina sintered body, the slide glass and the platinum was used as the base material for forming the barium titanate thin film was explained, but the present invention is not limited to these. The present invention can be widely applied when a barium titanate thin film is formed on a substrate made of the above material or a foil other than the substrate as a substrate.
【0028】また、基材を水溶液に浸漬することにより
チタン酸バリウム薄膜を形成するので、基材が複雑な形
状を有している場合にも、その表面にチタン酸バリウム
薄膜を確実に形成することができる。Further, since the barium titanate thin film is formed by immersing the base material in an aqueous solution, the barium titanate thin film is surely formed on the surface of the base material even if the base material has a complicated shape. be able to.
【0029】[0029]
【発明の効果】上述のように、この発明のチタン酸バリ
ウム薄膜の形成方法は、バリウムイオン及びチタンのア
ルコキシドを含有する水溶液に基材を浸漬することによ
り、該基材の表面にチタン酸バリウム薄膜を形成するよ
うにしているので、水溶液に基材を浸漬するだけで、容
易かつ経済的に、基材表面の広い面積に緻密で均一な強
誘電性のチタン酸バリウム薄膜を形成することができ
る。As described above, in the method for forming a barium titanate thin film of the present invention, a barium titanate is formed on the surface of a base material by immersing the base material in an aqueous solution containing barium ions and titanium alkoxide. Since a thin film is formed, it is possible to easily and economically form a dense and uniform ferroelectric barium titanate thin film on a large area of the substrate simply by immersing the substrate in an aqueous solution. it can.
【0030】また、基材を構成する材料の種類や、基材
の形状を問わず、基材表面にチタン酸バリウム薄膜を直
接形成することが可能になるため、基材を構成する材料
や形状の選択の自由度が向上し、さらにその応用分野を
拡大することができる。Further, the barium titanate thin film can be directly formed on the surface of the base material regardless of the type of the base material and the shape of the base material. The degree of freedom in selection can be improved, and its application field can be further expanded.
Claims (5)
i)のアルコキシドを含有する水溶液に基材を浸漬する
ことにより、該基材の表面にチタン酸バリウム薄膜を形
成することを特徴とするチタン酸バリウム薄膜の形成方
法。1. Barium (Ba) ions and titanium (T)
A method for forming a barium titanate thin film, which comprises forming a barium titanate thin film on the surface of the substrate by immersing the substrate in the aqueous solution containing the alkoxide of i).
タン(Ti)のアルコキシドをそれぞれ、Ba2+,Ti
(IV)に換算して、 Ba2+ :0.01〜150mM/l Ti(IV):0.01〜500mM/l の範囲で含有することを特徴とする請求項1記載のチタ
ン酸バリウム薄膜の形成方法。2. The aqueous solution contains barium (Ba) and titanium (Ti) alkoxides as Ba 2+ and Ti, respectively.
The barium titanate thin film according to claim 1, characterized in that, in terms of (IV), it is contained in the range of Ba 2+ : 0.01 to 150 mM / l Ti (IV): 0.01 to 500 mM / l. Forming method.
範囲にあることを特徴とする請求項1または2記載のチ
タン酸バリウム薄膜の形成方法。3. The method for forming a barium titanate thin film according to claim 1, wherein the temperature of the aqueous solution is in the range of 50 to 110 ° C.
とを特徴とする請求項1,2または3記載のチタン酸バ
リウム薄膜の形成方法。4. The method for forming a barium titanate thin film according to claim 1, wherein the pH of the aqueous solution is 13 or more.
アルカノールアミン変性したアルコキシドであることを
特徴とする請求項1記載のチタン酸バリウム薄膜の形成
方法。5. The titanium (Ti) alkoxide is
The method for forming a barium titanate thin film according to claim 1, which is an alkanolamine-modified alkoxide.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP31549791A JP3235145B2 (en) | 1991-11-01 | 1991-11-01 | Method of forming barium titanate thin film |
FR9212890A FR2683389B1 (en) | 1991-11-01 | 1992-10-28 | PRODUCTION OF THIN FILMS OF BARIUM TITANATE. |
DE19924236551 DE4236551B4 (en) | 1991-11-01 | 1992-10-29 | Production of barium titanate thin films |
US07/969,027 US5328718A (en) | 1991-11-01 | 1992-10-30 | Production of barium titanate thin films |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP31549791A JP3235145B2 (en) | 1991-11-01 | 1991-11-01 | Method of forming barium titanate thin film |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH05124817A true JPH05124817A (en) | 1993-05-21 |
JP3235145B2 JP3235145B2 (en) | 2001-12-04 |
Family
ID=18066082
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP31549791A Expired - Fee Related JP3235145B2 (en) | 1991-11-01 | 1991-11-01 | Method of forming barium titanate thin film |
Country Status (4)
Country | Link |
---|---|
US (1) | US5328718A (en) |
JP (1) | JP3235145B2 (en) |
DE (1) | DE4236551B4 (en) |
FR (1) | FR2683389B1 (en) |
Cited By (5)
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WO2007074875A1 (en) * | 2005-12-28 | 2007-07-05 | Showa Denko K. K. | Complex oxide film and method for producing same, composite body and method for producing same, dielectric material, piezoelectric material, capacitor and electronic device |
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JP3225583B2 (en) * | 1992-04-10 | 2001-11-05 | 株式会社村田製作所 | Barium titanate thin film forming method |
US5624604A (en) * | 1994-05-09 | 1997-04-29 | Yasrebi; Mehrdad | Method for stabilizing ceramic suspensions |
US5962654A (en) * | 1998-01-30 | 1999-10-05 | International Business Machines Operation | Alkoxyalkoxides and use to form films |
US6002031A (en) * | 1998-09-04 | 1999-12-14 | International Business Machines Corporation | Metal alkoxyalkoxidecarboxylates and use to form films |
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US3002861A (en) * | 1957-06-07 | 1961-10-03 | Lydia A Suchoff | Method of producing a coating of barium titanate |
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US4764493A (en) * | 1986-06-16 | 1988-08-16 | Corning Glass Works | Method for the production of mono-size powders of barium titanate |
FR2617151B1 (en) * | 1987-06-29 | 1990-10-12 | Solvay | PROCESS FOR THE MANUFACTURE OF MIXED METAL OXIDE POWDER, AND MIXED METAL OXIDE POWDERS |
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JPH01286922A (en) * | 1988-05-12 | 1989-11-17 | Toray Ind Inc | Method for forming barium titanate thin film |
FR2636060A1 (en) * | 1988-09-02 | 1990-03-09 | Thomson Csf | PROCESS FOR PRODUCING HYBRID CHEMICAL CERAMIC MATERIAL AND MATERIAL OBTAINED |
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-
1991
- 1991-11-01 JP JP31549791A patent/JP3235145B2/en not_active Expired - Fee Related
-
1992
- 1992-10-28 FR FR9212890A patent/FR2683389B1/en not_active Expired - Fee Related
- 1992-10-29 DE DE19924236551 patent/DE4236551B4/en not_active Expired - Fee Related
- 1992-10-30 US US07/969,027 patent/US5328718A/en not_active Expired - Lifetime
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Also Published As
Publication number | Publication date |
---|---|
US5328718A (en) | 1994-07-12 |
FR2683389B1 (en) | 1995-11-17 |
FR2683389A1 (en) | 1993-05-07 |
DE4236551A1 (en) | 1993-05-06 |
DE4236551B4 (en) | 2004-06-09 |
JP3235145B2 (en) | 2001-12-04 |
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